Stilbene dyestuffs and process for their manufacture



Patented Oct. 2, 1945 2,385,862 NT OFFICE 1 STILBENE DYESTUFFS AND PROCESS FO THEIR MANUFACTURE Ernst Keller, Basel, Switzerland, assignor to J. R. Geigy A. G., Basel, Switzerland, a firm No Drawing. Application January 16,1942, Serial 15 Claims.

It is known to condense dinitro stilbene disulionic acid, dinitrodibenzyl disulfonic acidor conversion products of p-nitrotoluene sulfonic acid with aromatic amino compounds especially aminoazo dyestuffs in various proportions and under various conditions in the presence of alkalis.

It has now been found in a surprising manner that according to the above reaction valuable new condensation products are obtained by wholly or partly replacing the known amino compounds by amino diaryl triazols, which contain at least one sulfonic acid group and/ or carboxylic acid group. It is immaterial to which of the two aryl radicals the amino group is bound. Only one or both aryl radicals may contain sulfonic acid and/or carboxyl groups and, if necessary, suitable further substituents, the sole condition being that the aminoaryl radical only contains substituents in positions which do not prevent the condensation. The condensation of these amino compounds with dinitrostilbene disulionic acid or analogues thereof may be effected in various ways. There are mentioned particularly: reaction by reflux or under pressure; use of the condensation components in molecular or suitable proportions; use of mixtures of aromati amino compounds already used for this reaction with the amino triazol derivatives now proposed according to the invention or mixtures of the last mentioned compounds.

Particularly important among the aforesaid amino compounds arethe amino azo dyestuffs which in o,o-position to the azo group contain metallisable substituents or their metal complex compounds, especially copper complex compounds, as for instance described in applicants U. S. patent application Ser. No. 293,483, filed September 5, 1939, now Patent No. 2,276,202, and

U. S. patent application Ser. No. 427,061, filed on,

even date herewith, now Patent No. 2,333,427. The condensation products may also be treated in known manner with oxidising and/or, in so far as metallisable groups are present, with metal-yielding agents.

Hereinafter some triazols which are used according to the invention are mentioned:

2 (4" aminophenyl) (naphtho-l'z2'z4z5-triazol) -4' :8-disul honic acid, 2 (4" aminophenyl)-(naphtho-1':2':4;5-triazol) -3:8-disulfonic acid, 7 2 (3" aminophenyD-(naphtho-l':2:4:5 -triazol) :7 disulfonic acid,

2 (4" aminophenyl)-(naph-tho-1:2':4:5-triazol) -5':7'- disulfonic acid,

2 (4" aminophenyl)-(naphtho-1':2":4:5-triazol) 3' :6 :8-trisu1fonic acid.

According to known methods of production (see, for example, Beilstein, vol. 26, page 318, and also German Patent No. 174,548 according to which the compound of the formula In Switzerland November 28,

NHa

is prepared, it is possible to produce the following compounds not described hitherto in publications: I

2 aminophefiyl)-(naphtho-1"z2'z4z-5-triazol) -6'1: 8'-disulfonic acid,

2 (4" aminophenyD-(naphtho-l':2:4:5-triazol) -4'-sulfonic, acid,

2 (4 -aminophenyl) -(naphtho-l':2':-4:5-triazol)-6-sulfonic acid, a

2 (4" amino 2" sulfophenyl) (naphtho- 2 (4 amino 2" sulfophenyl) (naphtho- 1' 2 4 5-triazo1) -6-su1f0nic acid,

2 (3" amino 4" chlorophenyl) (naphtho- .1 :2 z4't5-triazol) -5-:7'-di-sulfonic acid,

2 (4" amino 2"'-methoxyphenyl) -naphtho- 1" :2 :4 g5-triazol) -6-su1fonic acid,

2 (3" amino 4" methylphenyl) -(naphtho- 1' :2, :4z5-triazol) -5' :7-disulfonic acid,

2 (4" amino-3-methyl-6"-methoxyphenyl)- (naphtho-l :2 :4 Z'5-t1aZ01) -6'-sulfonic acid,

2- and4 (4 amino- 6" sulfonaphthyl-l)- (naphtho- 1' :2 :4 5-triazol) -6-sulfonic acid.

From the series of benzo-triazols there are mentioned for example the following compounds, which can all he produced by the method which has become known for 5-amino-2-(4'-sulfophen yl) -1 :3-benzotriazol:

5-amino-2- (3'-sulfophenyl) -1:3- benzotriazo1,

5 amino 2 (4 methyl 3' sulfophenyl) 1:3-benzotriazo1,

5 amino 2 (2'24 dimethyl 6 sulfophen yl) l :3-benzotriazol,

5 amino 2 (2z5' dimethyl 4 sulfophen yl) -1:3-benzotriazol,

5-amino-2- (Bmarboxyphenyl) -1 :3-benzotriazol,

5 amino 2 (2'25' dlmethoxy 4' 'sulfo phenyl) -1 3-benzotriazol,

5 amino 2 (4' chloro 3' sulfophenyl).

1 3-benzotriazol,

5 amino 2:2 (4':8'- disulfonaphthyl) -1:3-

benzotriazol,

5 amino 2:1'-(4'-sulfonaphthyl)-1:3-benzotriazol,

5 amino (4 hydroxy -3' carboxyphenyl) -1: 3-benzotriazol,

5 amino 2 (4' hydroxy 3' carboxy 5' methylphenyl)-1:3-benzotriazol and so forth. When, in the production of the last two com- V sulfonaphthyl) -1:3-benzotriazol,

Be. and worked up in the usual manner.

pounds, oxidation is effected with copper salts, theinsoluble copper "complexes are formed di rectly. These complexes are preferably converted into the soluble alkali metal salts by reaction with alkali metal sulfides. 7

As other benzotriazols, which can be produced by the same method as -amino-1:2'-(5':7'-dithe following may be mentioned: I 1

5 amino 1:2' 4 (6 -,sulfonaphthyl) -.1:3 benzotriazol,

5 amino 1:1 (6' sulfonaphthyl) 1:3

benzotriazol, r

W 51 parts of 5-amino-1-(S' carboXyphenyI) -1:3-

7 benzotriazol and 47.4 parts of the sodium salt'of dinitrostilbene disulfonic acid are condensed for hours at boiling temperature in 800 parts of water and 200 parts of caustic. soda lye of 36 B.

and worked up as usual. The condensation product is again dissolved in 800 parts of Water and 200 parts of caustic soda lye of 36 B. and at 60-70 C. chlorine is introduced until the alkali is consumed. The dyestuff, separated by salting 5 amino 1:1 (4 sulfonaphthyl) 1:3

benzotriazol, V V 5 amino 1 (4. hydroxy 3' carboxyphenyl) -1:3-benzotriazol, I V 5 amino 1 (2 -'hydroxy 3 carboxyphen yl) -1:3-benzotriazol, v

7 5-amino-1- (4-sulfophen'yl) -1 3-benzotriazol,

5-amino-1- (3f -carboxyphenyl) -1:3-benzotria'zol,

5-sulfo-1-(4'-arninophenyl) -1:3-benzotriazol. The last compound can be produced for example by reduction of 2-nitro-4-su1fo-4f -acetylamino-diphenyl amine, followed by diazotising and saponification of theaq etyl amino group.; The'new dyestufis dye cotton in yellow, orange, brown-red, brown, olive and other shades. These are distinguishedfrom the dyeings produced with 4 of dinitrostilbene disulfonic acid are condensed 7 the known stilbene dyestuffs in general by strong- 7 1y improved'water fastness, in part by improved washing fastness, light fastness and dischargeability, in part by purer shades. j i 1 The present invention is illustrated by the following examples, the parts being by weight:

EXAMPLE 1 42 parts of 2-(4 "-aminophenyl)-(naphtho-' 1'z2'z4b5striazoll-5':7'-disulfonic acid and 23.7 parts'of the sodium. salt of dinitrostilbene disulfonicacid are heated to boiling in a' stirring vessel with 260 parts of water and parts of caustic soda lye of 36-B. for 15 hours under refluxb The condensation product is precipitated with sodium chloride and filtered off. 'Itiis' dissolved in '200 parts of water and 10 parts of caus- 4 tic'soda lye of 36 B., 100. parts'of sodium hypochlorite (12% active chlorine) are added, heated for 3 hours up to 90-100 C. and after the reaction is finished, salted out with sodium chloride.

The dried dyestuff constitutes an orange powder; it dissolves in water'with a yellow color, in

V concentrated sulfuric acid with a blue-red color and dyes cotton in light fast reddish yellow shades. V V

A similar dyestuif is obtained when in the above examples 47.4 parts instead of 23.7 parts of the sodium'salt of dinitrostilbene disulfonic acid areout, constitutes," when dried, a red-orange powder; it dissolves in water with a yellow color, in concentrated sulfuric acid with a blue-red color and dyes cotton in light fast yellow shades.

When in the above example only 30 parts, instead off51 parts, of- 5-amino-1-(3-carboxyphenyl) 1:3-benzotriazol are used a similar more reddish dyeing dyestuffis obtained.

' EXAMPLE 4 V 25.4 parts of 5-amino-2-i3 carboxyphenyl) 1:3-benzotriazol and 47.4 parts of the sodium salt in an autoclave'for 8 hours'at 120-130C. with 500 parts of water and SO parts of caustic'soda' lye of 36 B.;[after neutralising with hydro-- chloric acid complete precipitation is efiected with sodium chloride. f

The dried dyestuff constitutes an orange-brown powder; it dissolves inQwater. with a Ibrownorange color, in concentrated sulfuric acid with a blue-violet color and dyes cotton in 'lightfast reddish-brown shades.

EXAMPLE 5 42 parts or 2- (4 "-aminophenyl)Khaphthm lz2 'z4r5-triazole) -5':7'-disulfonic acid, 34 parts of 2 (4;-aminopheny1) -(naphtho-1' :2 :4z5-triazol)-6'-s ulfonic acid and 47.4 parts otthe scdium salt ofdinitrostilbene disulfonic acidv are condensed for 12-15' hours by reflux with 500 parts of water and 30 parts of caustic soda lye 36 B. and the condensation product is ,worked upintheusualway; p x The'dyestuif constitutes an orange-brown powder; it dissolvesin water yellow, in concentrated sulfuric acid blue-red and dyes cotton in lightfast reddish yellow shades. I

When the dyestuff is treated with sodiumhypochlorite, for example as indicated in Example 1, a dyestuff of similar properties is obtained, which 5 dyes cotton in somewhat purer, greenish. yellow shades.

EXAMPLE 6 30 parts of- 2-(4"--aminophenyl)-(naphtho- 1 :2:4:5-triazole)-6'-sulfonic acid, 31 parts of the dyestuif m-amino-benzoic acid-+2z5-dimethoxy aniline and 47.4 parts of. the sodium saltof dinitrostilbene disulfonic acid are condensed by boiling for 12-15 hours with 700. parts of water and 120 parts of caustic soda lye of 36 B.

The condensation product, isolated in the usual 7 way, is dissolved in 500 parts of water and 30 parts of. caustic soda lye and heated during 3-4 hours up to 90-100 C. with. 300 parts of sodium I hypochlorite (12% active chlorine).

When the dyestufi is treated with sodium hypochlorite, for example as indicated in Example 1,"a product is obtained which dyes cotton in pure, yellowish orange shades.

vThe dyestuff thus purified constitutes a brown powder; it dissolves in water with a red-orange color, in concentrated sulfuric'acidwith a violet color and dyes cotton in lightfast' yellowish red shades. I

EXAMPLE 7 25 parts of the saponified dyestufi' p-amino;

acet-anilide salicylicacid, 27 parts of -amino- 2-(4'-hydroxy-3'-carboxy-phenyl) 1:3 benzotriazol and 47.4 parts of the sodium salt,- of dinitrostilbene disulfonic acid are condensed at boiling temperature for -18 hours with 800 parts of water and 200 parts of caustic sodalye of 36 B. The condensation product is isolated in the usual way.

The dyestuff, a brown powder, dissolves in water with a brown-orange color, in concentrated l0 sulfuric acid with a blue color and dyes cotton in brown-orange shades which by after-treatment with copper salts pass into red-brown shades, and by after-treatment with chromium salts into yellow brown shades, whilst at the same time the Washing-and water fastness is proved.

EXAMPLE 8 18 parts of the dyestutr 2-amino-1-hydroxybenzene-l-sulfonic acid- 2z5-dimethoxy aniline, 42 parts of 2-(4"-aminophenyl) (naphtha- 1':2:4:5-triazol)-5':7'-disulfonic acid and 47.4 parts of the sodium salt of dinitrostilbene disulfonic acid are condensed by boiling for 12-15 hours with 500 parts of water and 80 parts of caustic soda lye of 36 B. The drawn on deposite, precipitated with sodium chloride, is again dissolved in 800 parts of water, then a solution of 14 parts of copper sulfate in 60 parts .of water and 30 parts of ammonia is allowed to flow in at 80-90 C. and the whole heated for 12-15 hours to 90-95 C. The metallised dyestufi is precipitated with sodium chloride and filtered off; it constitutes, when dried, a black powder, which dissolves in water with a yellowolive color, in concentrated sulfuric acid with a violet color and dyes cotton in lightfast yellowolive shades.

When in the above example, for example parts, instead of 18 parts, of the dyestufi 2-amino-1-hydroxy-bcnzene-4-sulfonic acid-+215 dimethoxy aniline are used, the procedure being otherwise the same as above indicated, a dyestufi is obtained which dyes cotton, in more greenish olive shades of similar properties.

42 parts of the copper compound of the dyestufi 2 amino 1 hydroxy benzene-i-sulfonic acid- 2:5-dimethoxy-aniline, 27 parts of fi-amino- 2-(4'hydroxy-3 -carbo xy-phenyl) 1 3-benzotriazol and 47.4 parts of the sodium salt of dinitrostilbene disulfonic acid are condensed by reflux for 12-15 hours in 650 parts of water and 150 parts of caustic soda lye of 36 B.; after cooling neutralisation to an almost neutral reaction is efiected with hydrochloric acid and treated with sodium chloride.

The isolated dyestufi constitutes a dark powder; it dissolves in water with a reddish-brown color, in concentrated sulfuric acid with a bluered color and dyes cotton in lightfast brown shades, of which the water and washing fastness becomes improved by after treatment with copper salts.

EXAMPLE 10 47 parts of 2-(4"-amino-6"-sulfonaphthy1-1) (naphtho-l' :2 :4 5-triazol) -6-sulfonic acid and 23.7 parts of the sodium salt of dinitrostilbene disulfonic acid are condensed by boiling with 260 parts of water and parts of caustic soda lye 36 B. for 12-15 hours. The condensation product isolated in the usual manner is dissolved in 400 parts of water andv 30 parts of caustic soda lye 36 B. and heated for 2 hours up to -80 C. with parts of sodium hypochlorite. The dyestuif constitutes, when dried, a brown powder which dissolves in water with an orange coloration, in concentrated sulfuric acid with violet col-L oration and dyes cotton with lightfast orange shades. e y

A similar dyestufl is obtained by using 40 parts instead of 23.7 parts of the sodium salt of dinitrostilbene disulfonic acid.

dinitrostilbene disulfonic acid are given.

Table I Condensation ratio between D tt i am 19' amino coma yeing on co on Nd Ammo compound pound and (b) siter-coppered dinitrostilbene disullonic acid ll 2-(3-ami.nophenyl)-(naphtho-1':2 :415-tria2ol)-5:7-disulfonic acid (a) llgeddish' yellow. 12 .do o. I l3 2-(4-aminophenyl)-(naphtho-l:2:4:5-triazol)-G-sulfonic ac id Do, 14 2-(4"-aminophenyl)-(naphtha-1:2:4:5-triazol)-4-sulfon1c acid Do. 15 2-(4-aminophenyl)-(naphtho-l:2:4:5-tr1azol)-6:8-d sulfon1c ac1d Do, 16 2-(4-aminophenyl)-(naphtho-1:2:4:5-triazol)-4:-dlsulfonic acid Do. 17 2-(4-amino-2-sulfophenyl)-(naphtho-l:2:4:5-tr1azol) (a) gfllow, 18 d l do 6-amino-2- (4-hydr0xy-3-carb oxyphenyl) -1 :3-benzotriazol 5-amino-2- (4'-methyl-3-suliophenyl)-l :3-benzotriazol 5-amino-2-(3':6-dimethyl-4-suliophenyl)-1:B-benzotnazol 5-sulfo-l-(4-aminopheny1)-1:3-benzotriazol o. (a) Yellow-orange. (a) Reddishyellow. (a) Orange.

H (a) Yellow-orange.

Do. (a) I]t)eddish-yellow.

o. (a) Brown-orange,

(11) Orange.

(41) Orange. Do. Do.

(b) yellow-brown.

o. (a) Yellow-orange.

In the following Tables-II and III there are one molecule of dinitrost'ilbene 'disulfonic acid.

group consisting of thesulfo and carboicy radi;

V cals and being-free from N=N'-groups.--

2.'In themanufactureof stilbene dyestuffs by condensation of -'dinitrostilloen'e disulfonic acid,

According to theinvention the condensation may} 5 dinitrodiloenzyl disulfonic acid or p-nitrotoluene however, be effected in other suitable ratios besulfonic acid with aromatic compounds, which tween'at least 1 molecule and atmo-st 2 molecules contain free amino groups, in any dSiT6d"pI0f of amino compound per molecule'of 'dinitrostil portion, in presence of caustic alkalis, withor V bene' disulfonic acid. without the'application of'pressure,-an'd it de- TabZeII fi z f 1st amino compound I amino compound j 's Z g;:: g 2-(4-aminophenyl) (naphtho-l' :2 :5-t1iaz0l)- 5':7-disulfonic acid Dehydrothio p-toluidine-sulfonic acid. (a) Reddish-yel low. ..do Su1fanilic'acid-' 1-amino-3 (a)ran methyl-G-methoxy-benzene. 7

do m-Aminobenzoic acid 2 :-di- (a) Red-orange. V Inethoxy aniline.

2-(4-aminophenyl)-(naphtho-1':2:4:5-triazol)-6-su1fonicacid;. Sulfafirilicacid 2:5-din1ethoxy Do.- an1ne. do -Q .e m-Aminobenzoic acid. l-amj- ((1) Orange.

no-B-methyl-dmethoxy-benzene.

5-amino-l-(3-carboxyphenyll-l:3-benzotriazol 2-(4 -an1inopl1eny1) -(naphtho-1 :2 z kfi-tria zol) 5 :7-disulfonic acid.

m-Aminobenzoic acid- 2:5-dimethoxy-aniline.

p'-Arninoacet-'anilide salicylic '(a) (a) Red-orange.

Brown-orange,

. I Y acid, saponified. V (b) brown-. r 2-(4-aminophenyl)-(naphtho-1:2. :5-triazo1)-6-sulfonic acid do Do. 7 do r p-Aminoacet-anilide o-creso- Do.

. tinic acid, saponified V '5-amino-1 (4-hydroxy-3'-carboxyphenyl)-l:3-benzotriazol p-Aminoacet-anilide salicylic Do.

' 1 acid, saponified. 5-amino (2-l1ydroxy-3-carboxy-4-sulfophenyl)-1:3-benz0tr1azol. do 1 Do,

Table III p I Dyeing of the copper Example 1st amino compound 2nd'am1no compound complex compound N on cotton ionic acid.

fOIllC acid.

2 -amino-khydroxybenze1ie-4-sulfonic Violetisli-brown.

* acld m-anisidine. do Do.

2-amino-l-hydroxybenzene-4-sulionic Brown.

acid m-anisidine. 2-amino-fi-chloro-l-hydroxybenzene- Do.

4-sulfom'c acid m-anisidine. 2amin'olhydroXybenzeneA-sulfonic Olive.

acid 2:5-dimethoxy-aniline. D o o.

4-nitr0-2-amino-l-hydroxybenzene Reddish-brown.

m-anisidine. 4-nitro2aminolhydroxybenzene 2:5-dimethoxy-aniline. 4-nit'ro-2-amino-1-hydroxybenzene 5 3amino-C-phenyl1 :2N th1azo1o5hydroxynaphthalene sulifonic acid.

Brown.

Instead of the tria zols cited in the above eX- sired suloseduent treatment of the products with amples and tables there may also equally well [be general part of the specification.

What I claim is:

1. In the manufacture of stilbene dyestufis by condensation of dinitrostilbene di'sulfonic acid, dinitrodibenzyl disulfonic acid or p-nitrotoluene used the other compounds enumerated in the metal yielding and/or oxidising agents, the improvement wherein instead of up to two molecules of the "known aromatic amino compounds there are used on one molecule of a compound selected from the group consisting of dinitro- --stilbene disulfonic acid, dinitrodibenz'yl disulsulfonic acid with aromatic compounds, which contain free amino groups, in any desired proportion, in presence of caustic alkalis, with or Without the application of pressure, and if desired subsequent treatment of the products with ionic. acid and-p-nitrotoluene sulfonic acid together with other amino compounds whose use for this condensation is known, at least one mole-.

cule of an aminoaryltriazol of the benzene and naphthalene series containing in one ofthe positions 1 and .2 of the triazol ring an aryl radical selected from the group consisting of aryl radicals of the benzene andnaphthalene series, said groups.

from the group consisting of aryl radicals of the benzene and naphthalene series, said amino,- aryltriazol containing at leastone member of the aminoaryltriazol containing at least one mem ber of-the group consisting of the sulfo and car-g boxy radicals and; being free from -N=N-- 3. In the manufacture of stilbene dyestuffs by, condensation of dinitrostilbene disulfonic acid, (11 nitrodibenzyl disulfonic acid or p-nitrotoluene sulfonic' acid with aromatic compounds, which contain free amino groups, in any'.desiredproportion, in presence of caustic amass, with or without the application of pressure, and if desired subsequent treatment of the products with metal yielding and/or oxidising agents, the improvement wherein instead of up to two molecules of the known aromatic amino compounds there are used on one molecule of a compound selected from the group consisting of dinitrostilbene disulfonic acid, dinitrodibenzyl disulfonic acid and p-nitrotoluene sulfonic acid together with metallisable aminoazobenzene compounds whoseuse for this condensation is known, at least one molecule of an aminoaryltriazol of the benzene and naphthalene series containing in one of the positions 1 and 2 of the triazol ring an aryl radical selected from the group consisting of aryl radicals of the benzene and naphthalene series, said aminoaryltriazol containing at least onemember of the group consisting of the sulfo' and carboxy radicals and being free from N=N groups, and metallizing the so-obtained, condensation product.

4. In the manufacture of stilbene dyestuffs by condensation of dinitrostilbene disulfonic acid, dinitrodibenzyl disulfonic acid, p-nitrotoluene sulfonic acid with aromatic compounds, which contain free amino groups, inany desired proportion, in presence of caustic alkalis, with or without the application of pressure, and if desired subsequent treatment of the products with metal yielding and/or oxidising agents, the improvement wherein instead of the known aromatic amino compounds there are used aminonaphthotriazols which are free from N=N- groups and which correspond to the formula wherein 11 means one of 1, 2 and 3, the benzene radical containing besides the amino group substituents selected from the group consisting of H, Cl, CH3, OCI-Ia and SOaH.

5. In the manufacture of stilbene dyestuffs by condensation of dinitrostilbene disulfonic acid, dinitrodibenzyl disulfonic acid, p-nitrotoluene sulfonic acid with aromatic compounds, which contain free amino groups, in any desired proportion, in presence of caustic alkalis, with or without the application of pressure, and if desired subsequent treatment of the products with metal yielding and/r oxidising agents, the improvement wherein instead of the known aromatic amino compounds there are used aminobenzotriazols of the formula the benzene radical A containing substituents selected from the group consisting of H, CH3, OCHs, Cl, OH, COOH and SOzH, said aminobenzotriazols containing at least one member of the group consisting of the sulfo and carboxy radicals and being free from N=N groups.

6. In the manufacture of stilbene dyestuffs the step of condensing at most two molecules of 2-(4"-aminopheny1) (naphtho 1' :2:4:5 triazol) -5':7-disulfonic acid with one molecular proportion of dinitrostilbene disulfonic acid.

7. In the manufacture of stilbene dyestufis,

the steps ofvcondensing one molecular proportion of l with one molecular proportion of dinitrostilbene disulfonic'acid and coppering the condensation product.

8; In the manufacture of stilbene dyestuffs, the

steps of condensing one molecular proportion 'of and one molecular proportion of OOH:

I .0 CH3 'with one molecular proportion of dinitrostilbene disulfonic acid and coppering the condensation product.

9. A new stilbene dyestuff from the condensation with dinitrostilbene disulfomc acid of an amino diaryl triazol free from- N=N-- groups and selected from the amino diaryl triazols of the benzene and naphthalene series containing at least one member of the group consisting of the sulfo and carboxy radicals and, in one of the positions 1 and 2 of the triazol ring, an aryl radical selected from the group consisting of aryl radicals of the benzene and naphthalene series, the other aryl radical of the amino diaryl triazol being free from hydroxy groups.

10. A new stilbene dyestufi from the condensation with dinitrostilbene disulfonic acid of an amino compound and an amino diaryl triazol free from N=N- groups and selected from the amino diaryl triazols of the benzene and naphthalene series containing at least one member of the group consisting of the sulfo and carboxy radicals and, in one of the positions 1 and 2 of the triazol ring, an aryl radical selected from the group consisting of aryl radicals of the benzene and naphthalene series, the other aryl radical of the amino diaryl triazol being free from hydroxy groups.

11. A new stilbene dyestufi from the condensation with dinitrostilbene disulfonic acid of an aminotriazol of the formula stituents selected from the group consistingof I-I, Cl, CH3, OCI-Is and SOsH, said aminotriazol being free from -N=N groups.v

12. A new Stilbene dyestufi from the condensation with 'dinitrostilbene disulfonic acid of an aminotriazol of the formula HzN the benzene radical A containing substituents selected {from the group consisting of H, CH3, OCHs, C 1, OH, COOH and SOsI-I, said aminotriazol containing at least one member of the group consisting of the sulfo andcarboxy radicals and benitrostilbene disulfonic acid of one molecular proportion of V d one molecular proportion of said dyestufi being; in the form: of the sodium o salt 'a brown powder, dissolving in water with a brown-orange color, in concentrated sulfuric acid with a blue color and dyeing cotton in brownorange shades which by after-treatmentwwith copper salts pass into red-brown shades of improved waterand'washing fastness... f

15. The new stilbene' dyestufi fromthe c'ondensation withone. molecular proportion of di nitrostilbene disulfonic acid of one molecular prov-4 portion of SOaH Hols /N V H I V N VNH: V

N p r and one molecular proportion of sour OOH! and treatment with a copper salt, said dyestufi; being in the form of the sodium salt a black powder,-disso1ving in water with a yellow olive color, in concentrated sulfuric acid with a -violet color and dyeing cotton in lightfast yellow olive.

shades. r

ERNST KELLER. 

